Preparation of water-reducing copolymers for concrete

ABSTRACT

Alkoxylated acrylate and methacrylate macromonomers are disclosed that are useful in the preparation of water-reducing additives for concrete, ultraviolet light-curable adhesives, and water-dispersed polyurethanes. The macromonomers are suitably prepared by alkoxylating a hydroxyalkylacrylate or hydroxyalkylmethacrylate in the presence of a DMC catalyst using the continuous addition of starter (CAOS) in order to prevent the formation of by-products during the fabrication of the macromonomer.

FIELD OF THE INVENTION

[0001] This invention relates generally to alkoxylated acrylate andmethacrylate macromonomers useful for preparing water-reducing additivesfor concrete, ultraviolet light (UV)-cured adhesives, andwater-dispersed polyurethanes. The macromonomers are prepared using thecontinuous addition of starter in order to minimize the by-productformation during the alkoxylation reaction used to produce themacromonomer.

BACKGROUND OF THE INVENTION

[0002] Polyols produced using a double metal cyanide (DMC) catalyst areknown to possess advantageous properties, such as low ethylenicunsaturation. Particularly preferred polyols made using these DMCcatalysts are produced using a continuous addition of starter, togetherwith optional initially charged starter, during the polymerization ofepoxide to produce the desired polyol, as described in more detail inU.S. Pat. No. 5,777,177. The '177 patent teaches the use of water or alow molecular weight polyol as the starter, and discloses that theresulting polyol has a reduced amount of high molecular weight tail.

[0003] The continuous addition of other starters, such ashydroxypropylmethacrylate (HPMA) to initiate the polymerization of anepoxide, such as propylene oxide or ethylene oxide, in the presence of aDMC catalyst, is described in U.S. Pat. No. 5,854,386, notably at column3, lines 13-16, and column 6, lines 15-18 thereof. The '386 patentdiscloses that this methodology is useful in preparing stabilizers forpolymer polyols and impact modifiers made by reacting the stabilizerwith one or more polymerizable vinyl monomers. This process is describedin more detail in the paragraph bridging columns 7 and 8 of that patent.The '386 patent is incorporated herein by reference in its entirety.

[0004] Due to the hydrophobic nature of many polyurethanes, there is aneed to employ a dispersion stabilizer when preparing water-dispersedpolyurethanes in order to prevent the dispersion from “breaking” byvirtue of precipitation or agglomeration of the polyurethane component.Conventional dispersion stabilizers for water-dispersed polyurethanesare typically expensive, and oftentimes do not perform as well as mightbe desired. For example, 2,2-dimethyol propionic acid (DMPA) is costly,in short supply, and typically does not provide acid groups in thedesired location on the urethane molecule, namely in the middle of thehydrophobic polyether portion of the molecule, upon reaction with anisocyanate.

[0005] There currently is a need in the polyurethanes manufacturingcommunity for inexpensive, homogeneous macromonomer compositions thatare useful in preparing water-dispersed polyurethanes having alcoholwater-dispersing moieties in a middle portion of the urethane molecules.The present invention provides one solution to this need by using“continuous addition of starter” (CAOS) methodology to preparealkoxylated macromonomers, such as propoxylated acrylate- andpropoxylated methacrylate-macromonomers. These macromonomers can becopolymerized with an acid, or combination of acids, to produce astabilizer for water-dispersible polyurethanes. Alternatively, thesemacromonomers can be co-polymerized with a monomer, or combination ofmonomers, to produce copolymers that are useful as additives inconcrete-forming compositions. These additives permit the use of areduced amount of water in fabricating the concrete, and provide afurther improvement over the water-reducing agents described inco-pending U.S. application Ser. No. 09/358,009 filed Jul. 21, 1999.These copolymers are also useful as additives in UV-curable adhesives inorder to enhance the adhesive's performance.

SUMMARY OF THE INVENTION

[0006] One aspect of this invention provides an improved process forproducing an alkoxylated acrylate macromonomer or an alkoxylatedmethacrylate macromonomer. The alkoxy moiety of the macromonomercontains between one and six carbons. In the process, a first component,namely a hydroxyalkylacrylate or a hydroxyalkylmethacrylate, is reactedwith a second component, namely an alkylene oxide compound (preferablyan alkylene oxide selected from the group consisting of ethylene oxide,propylene oxide, butylene oxide, and combinations thereof). Themacromonomer is produced by co-feeding the reactants into the reactionvessel co-currently or counter-currently, and carrying out the reactionat a reaction temperature of between about 60° C. and about 130° C. inthe presence of a DMC catalyst, and optionally in the presence of asolvent. The reaction employs a CAOS method whereby the first componentis added to a reactor already containing at least some amount of thesecond component. Use of this CAOS method facilitates production of thedesired macromonomer, and reduces the likelihood of forming unwantedbyproducts.

[0007] In another aspect, the present invention comprisesco-polymerizing the above-described macromonomer with a monomer selectedfrom the group consisting of acrylic acid, methacrylic acid, fumaricacid, styrene, maleic acid, methyl methacrylate, and combinationsthereof. The resulting copolymer is useful as a water-reducing additivefor concrete formation. When this water-reducing additive is present ina reaction mixture comprising sand, cement, and water, less water isneeded than the amount that is necessary to prepare concrete in theabsence of the water-reducing additive.

[0008] In still another aspect, this macromonomer, and its derivatives,can be used as a performance-enhancing additive for a UV-curableadhesive.

[0009] In yet another aspect, the above-described macromonomer can beused in the preparation of water-dispersible polyurethanes. For thisuse, the macromonomer is co-polymerized with a monomer selected from thegroup consisting of acrylic acid, methacrylic acid, fumaric acid, maleicacid, and combinations thereof, in order to produce a co-polymercontaining hydroxyl and acid moieties. At least a portion of thehydroxyl moieties on the co-polymer are then reacted with an isocyanateto provide the water dispersible polyurethane.

[0010] These and other aspects of the present invention will becomeapparent upon reading the following detailed description of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

[0011] It has now been surprisingly found that macromonomers produced inaccordance with the present invention using a continuous addition ofstarter methodology are particularly useful in fabricatingwater-reducing additives for concrete-forming compositions, in producingdispersants for water-dispersible polyurethanes and performanceenhancing additives for UV curable compositions. Illustratively, themacromonomers are reacted with a vinyl monomer to produce a co-polymerthat is useful as a water-reducing additive (WRA) in concrete-formingcompositions.

[0012] The macromonomers are prepared at a relatively low reactiontemperature (between about 60 degrees and about 130 degrees Centigrade,preferably between about 60° C. and about 110° C.) in the presence of arelatively low concentration of a DMC catalyst (5 ppm to 500 ppm,preferably 5 ppm to 50 ppm), optionally in the presence of a solvent.The relatively low concentration of DMC catalyst, together with therelatively low reaction temperature, has been found by the presentinventor to reduce or minimize the homopolymerization of the acrylateand methacrylate reactants. These reaction parameters have also beenfound to reduce or minimize the transesterification of hydroxyalkylmethacrylate and hydroxyalkylacrylate to form unwanted di-methacrylateand di-acrylate by-products. These byproducts are undesirable since theywould be detrimental to the present inventor's envisioned use of themacromonomers as intermediates in the production of dispersants forwater-dispersed polyurethanes, as well as the other uses describedherein.

[0013] The macromonomers produced in accordance with the presentinvention are made using CAOS methodology wherein the methacrylate oracrylate “starter” is continuously added during the course of thereaction. The alkylene oxide compound employed in oxyalkylating the“starter” or “initiator” may be any alkylene oxide polymerizable withDMC catalysts.

[0014] Suitably, the alkylene oxide is selected from the groupconsisting of ethylene oxide, propylene oxide, butylene oxide, andcombinations thereof. Illustrative compounds include ethylene oxide,propylene oxide, 1,2- and 2,3-butylene oxide, C6-30 alpha-olefin oxides,glycidol, and halogenated alkylene oxides. Preferred are propylene oxideand ethylene oxide.

[0015] Mixtures of more than one alkylene oxide many be used, forexample, mixtures of propylene oxide and ethylene oxide. Alkyleneoxides, and their mixtures, may be polymerized onto the initiatormolecules in one or more stages, to produce homopolymers, blockcopolymers, random copolymers, block random copolymers and the like.“Copolymer” in the present application includes “terpolymer” andmixtures of more than three alkylene oxides as well.

[0016] Other co-monomers may be polymerized along with the alkyleneoxide. Examples of copolymerizable monomers include those disclosed inU.S. Pat. Nos. 3,278,457; 3,278,458; 3,404,109; 3,538,043; 3,900,518;3,941,849; 4,472,560; 5,145,833; and 5,223,583 which are hereinincorporated by reference. Glycidol is a particularly preferredcopolymerizable monomer, and it may be used to introduce additionalhydroxyl functionality.

[0017] Suitable DMC catalysts are well known to those skilled in theart. DMC catalysts are non-stoichiometric complexes of a low molecularweight organic complexing agent, and optionally other complexing agents,with a double metal cyanide salt, e.g. zinc hexacyanocobaltate.Exemplary DMC catalysts include those suitable for preparation of lowunsaturation polyoxyalkalene polyether polyols, as disclosed in U.S.Pat. Nos. 3,427,256; 3,427,334; 3,427,335; 3,829,505; 4,472,560;4,477,589; and 5,158,922. Preferably, however, the DMC catalysts used inaccordance with the preferred aspects of the present invention are thosecapable of preparing “ultra-low” unsaturation polyether polyols such aspolypropylene glycols and random EO/PO copolymers. The polyoxyalkylenepolymers produced by the catalysts typically have levels of unsaturation(other than the purposefully introduced unsaturation of the subjectinvention starter molecules) less than about 0.010 meq/g, as measured byASTM D-2849-69, “TESTING OF URETHANE FOAM POLYOL RAW MATERIALS”. Suchcatalysts are disclosed in U.S. Pat. Nos. 5,470,813 and 5,482,908, and5,545,601, and these patents are incorporated herein by reference intheir entirety. Preparation of the macromonomers of the presentinvention is facilitated using such highly active DMC catalysts.

[0018] Oxyalkylation conditions may be varied to suit the particularreactive unsaturation-containing initiator, alkylene oxide, and thelike. For example, with liquid or low melting initiators, oxyalkylationmay be effected by oxyalkylating neat, while with these same initiatorsor with solid initiators of higher melting point, oxyalkylation insolution or suspension in an inert organic solvent may be desired.Suitable solvents include aprotic polar solvents such asdimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone,dimethylformamide, acetonitrile, methylene chloride, and especially themore volatile hydrocarbon solvents such as benzene, toluene,ethylbenzene, cyclohexane, petroleum ether, methylethylketone,cyclohexanone, diethylether, tetrahydrofuran, and the like.

[0019] It has been found that certain hard-to-dissolve initiators may beinitially oxyalkylated in suspension in an organic liquid such astoluene, and following oxyalkylation with from 1 to 4 mols of alkyleneoxide, will form soluble reaction products which can be furtheroxyalkylated in solution.

[0020] Oxyalkylation temperatures and pressures are conventional whenemploying vinyl polymerization inhibitors. Temperatures may range fromroom temperature or below to about 150° C., or higher. Preferably,temperatures in the range of 70° C. to 140° C. are used, more preferablyabout 70° C. to 110° C. When highly active DMC catalysts capable ofproducing ultra-low unsaturation (less than 0.010 meq/g) are used, andthe reaction is conducted at a low temperature, i.e. below 110° C., andmost preferably in the range of 70° C. to 100° C., thenpolyoxyalkylation can occur at reasonable rates without additionalpolymerization of the unsaturated moieties present. This is true even inthe absence of a vinyl polymerization inhibitor. Alkylene oxide pressureis adjusted to maintain a suitable reaction rate, consistent with theability of the process system to remove heat from the reactor. Pressuresfrom 2 psia or lower to about 90 psia are useful. A pressure of 2 to 15psia, 2 to 10 psia when employing propylene oxide, ethylene oxide, or amixture of these alkylene oxides, may be advantageous.

[0021] Catalyst concentration is generally expressed as ppm based on theweight of the product. The amount of catalyst will depend upon theactivity of the particular DMC catalyst. When using very activecatalysts, such as those disclosed in U.S. Pat. Nos. 5,470,813;5,482,908; and 5,545,601, amounts from less than 5 ppm to 500 ppm orhigher are useful, more preferably from about 15 ppm to about 150 ppm.

[0022] In a typical synthetic procedure, the reaction is effected usinga continuous addition of the initiator during the course of the reactionas disclosed in copending U.S. application Ser. No. 08/597,781, herebyincorporated by reference. For example, the initiator or initiators maybe fed to the reactor continuously, either dissolved in alkylene oxide,dissolved in inert diluent, or, with liquid initiators, neat. Thecontinuous addition of the initiator(s) may also be accompanied bycontinuous removal of product, resulting in a continuous synthesisprocess, as disclosed in U.S. application Ser. No. 08/683,356, alsoincorporated herein by reference.

[0023] The oxyalkylation of the reactive-unsaturation containingmolecule is suitably conducted in the presence of a vinyl polymerizationinhibitor, preferably of the type which function without the presence ofoxygen, since oxyalkylations are generally “in vacuo”, meaning in thiscase that virtually the entire reactor pressure is due to alkyleneoxide; or in the presence of a gas inert to the process, e.g. argon,nitrogen, etc. In other words, the partial pressure of oxygen,generally, is substantially zero. It is common to flush oxyalkylationreactors with nitrogen one or more times prior to final evacuation andintroduction of alkylene oxide. Suitable inhibitors are well known tothose skilled in the art of vinyl polymerization. Suitable inhibitorsare, for example, butylated hydroxy toluene (BHT), 1,4-benzoquinone,1,4-napthoquinone, diphenylphenylhydrazine, ferric chloride, copperchloride, sulfur, aniline, t-butyl-catechol, trinitrobenzene,nitrobenzene, 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil), and thelike. BHT is preferred.

[0024] The inhibitor should be used in an amount effective to inhibitpolymerization of the reactive unsaturation-containing inhibitor. Thus,the amount will vary with the reactivity of the particular type ofunsaturation. Acrylates and methacrylates, for example may requirehigher levels of inhibitor than less reactive unsaturation-containinginitiators. The amount of inhibitor will also vary with oxyalkylationtemperature, with higher temperatures requiring higher amounts ofinhibitor. Amounts of inhibitor, in weight percent relative to theweight of the reactive-unsaturation containing initiator, may vary fromabout 0.01 weight percent to about 1 weight percent, and more preferablyfrom about 0.05 weight percent to about 0.5 weight percent. The latterrange is particularly useful with BHT. If the vinyl polymerizationinhibitor is not used, particularly with less active DMC catalysts, theproduct may be highly colored, or gelling of the product may occur.

[0025] Following oxyalkylation, the macromonomer may be vacuum stripped,for example using a stream of nitrogen, to remove unreacted monomers andother volatile components. The products may also be filtered to removetraces of DMC catalysts or their residues, or the products may besubjected to other methods of catalyst removal. When DMC catalysts ofthe ultra-low unsaturation-producing type are employed, the smallamounts of catalysts used may be left in the product, or the product maybe subjected to simple filtration to remove the catalysts and theirresidues.

[0026] The macromonomer is suitably reacted with a monomer such asacrylic acid, methacrylic acid, fumaric acid, styrene, maleic acid,methyl methacrylate, and combinations thereof, at a reaction temperatureof between about 0° C. and about 100° C., preferably between about 30°C. and about 60° C., to prepare products useful in a variety ofapplications.

[0027] Illustratively, the macromonomer thusly produced may be used toprepare the dispersant for water reducing admixture for concrete,polymer polyol, or water-dispersed polyurethanes by reacting theintermediate with a vinyl monomer, such as acrylonitrile, styrene,acrylic acid, methacrylic acid, methylmethacrylate, methylacrylate,p-methylstyrene, or the like. A vinyl polymerization initiator, e.g. anorganic peroxide, hydroperoxide, peroxyester, azo compound, ammoniumpersulfate, or the like, is optionally added, and polymerizationcommenced. Examples of suitable free radical polymerization initiatorsinclude acyl peroxides such as dihexanoyl peroxide and dilaurolylperoxide, alkyl peroxides such as t-butyl peroxy-2-ethylhexanoate,t-butylperpivalate, t-amylperoctoate,2,5-dimethyl-hexane-2,5-di-per-2-ethylhexoate, t-butyl-per-dodecanoate,t-butylperbenzoate and1,1-dimethyl-3-hydroxybutylperoxy-2-ethylhexanoate, and azo catalystssuch as azobis(isobutyronitrile), 2,2′-azo-bis-(2-methylbutyronitrile),and mixtures thereof. Ammonium persulfate and other water-solubleinitiators are preferred. Redox initiator systems are also suitable foruse in this invention.

[0028] The polymerization initiator concentration employed is notcritical and can be varied considerably. As a representative range, theconcentration can vary from about 0.1 to about 5.0 weight percent oreven more, based upon the total feed to the reactor. Up to a certainpoint, increases in the catalyst concentration result in increasedmonomer conversion, but further increases do not substantially increaseconversion. The particular catalyst concentration selected will usuallybe an optimum value considering all factors, including costs. It hasbeen determined that low concentrations can be used in conjunction withhigh potency preferred stabilizers while still obtaining the desireddispersants for water reducing admixture for concrete, water-dispersedpolyurethane, and polymer polyol.

[0029] In preparing water-dispersible polyurethanes, at least a portionof the hydroxyl moieties present on the co-polymer is suitably reactedwith an isocyanate. Any isocyanate may be employed, such as an aromaticisocyanate, i.e. toluene diisocyanate (TDI), or an aliphatic isocyanate,such as hexamethylene diisocyanate (HDI), or combinations thereof. Otheruseful isocyanates include isophorone diisocyanate (IPDI), ethylenediisocyanate, 1,4-tetramethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,10-decanemethylenediisocyanate, 1,12-dodecanemethylene diisocyanate,cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate,1-isocyanato-2-isocyanatomethyl cyclopentane, isophorone diisocyanate,bis-(4-isocyanatocyclohexyl)-methane, 1,3- and/or1,4-bis-(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane,4,4′-dicyclohexylmethane diisocyanate, and combinations thereof.

[0030] As used herein, all percents are by weight unless otherwisespecified, “ppm” designates “parts per million”, and all temperaturesare in “degrees Centigrade” unless otherwise specified.

[0031] The following examples are intended to illustrate, but in no waylimit the scope of, the present invention.

EXAMPLE 1 Preparation of Macromonomer A via a Total CAOS (ContinuousAddition of Starter) Process

[0032] To a 300-gallon stainless steel pressure reactor, 250 lbs. oftoluene (as a solvent), 245 g. BHT and 13.5 grams of DMC catalyst wereadded. The DMC catalyst is a zinc hexacyanocobaltate catalyst asproduced by Example 2 of U.S. Pat. No. 5,482,908; and this patent isincorporated herein by reference in its entirety. The reactor wasstripped with nitrogen at room temperature for 10 minutes. Afterstripping, the reactor was kept under vacuum and was heated up to 100°C. HPMA was then fed into the reactor at 0.141 lb/min while both PO andEO are fed at 0.918 lb/min respectively. After 18.4 lbs. PO was fed intothe reactor (20-min after the feeding started), all the feeds wereturned off, and the reactor was let to cook out. After the reactorreached half pressure, the reactor was cooled down to 90° C., all feeds(HPMA, EO, and PO) were resumed at the twice the previous feed rates.Finally, after 4 hrs feeding of HPMA, EO and PO, all the feeds wereclosed again for 30 minutes to cook out. Additional BHT (300 g) wasadded to the reactor and the reactor was stripped under full vacuum for3 hrs at 130° C. to remove the residual oxides and toluene. After thestripping, the reactor was cooled down and additional BHT (250 g) wasadded to the reactor. Finally the product, Macromonomer A, was drainedto the containers.

EXAMPLE 2 Preparation of Macromonomer B via a Total CAOS Process

[0033] To a 300 gallon stainless steel pressure reactor, 220 lbs.Macromonomer A, 490 g of BHT and 26.9 grams of DMC catalyst as describedin Example 1 were added. The reactor was stripped with nitrogen at 100°C. for 40 minutes. After stripping the reactor was kept under vacuum andwas maintained at 100° C. HPMA was then fed into the reactor at 0.144lb/min while both PO and EO were fed at 0.937 lb/min respectively. After18.74 lbs. PO was fed into the reactor (20-min after the feedingstarted), all the feeds were turned off, and the reactor was let to cookout. After the reactor reached half pressure, the reactor was cooleddown to 90° C., all feeds (HPMA, EO, and PO) were resumed at twice theprevious rates. Finally, after 8 hrs feeding of HPMA, EO and PO, all thefeeds were closed again for 30 minutes cook out. The reactor wasstripped under full vacuum for 30 minutes to remove the residual oxidesat 90° C. After the stripping the reactor was cooled down and additionalBHT (485 g) was added to the reactor. Finally the product, MacromonomerB, was drained to the containers.

COMPARISON EXAMPLE 3 Preparation of Macromonomer C via a Semi-BatchProcess

[0034] To a one-liter stainless steel pressure reactor, 54 g. of HPMA,50 g of toluene, 0.5 g. BHT, 0.2 g of benzoquinone, and 0.12 g DMCcatalyst as described in Example 1 were added. The reactor was strippedfor 5 minutes at room temperature. After stripping, the reactor was keptunder vacuum and was heated up to 100° C. Both PO and EO are fed intothe reactor at 1.5 g/min respectively. After 10 g of PO was fed into thereactor (6.5 minutes after the feeding started), both the EO and POfeeds were turned off, and the reactor was let to cook out. After thereactor reached half pressure, both feeds (EO and PO) were resumed atthe same feed rate of 1.5 g/min. Finally, after 4 hrs feeding of both EO(total of 348 g) and PO (total of 348 g), both the feeds were closedagain for 30 minutes cook out. The reactor was stripped under fullvacuum for 60 minutes at 100° C. to remove the residual oxides andtoluene. After the stripping, the reactor was cooled down. Finally theproduct, Macromonomer C, was drained to the containers.

[0035] Analytical Results Comparison of the Three Samples Sample ProcessDiol Viscosity OH# Mw/Mn Example 1 Total CAOS 0.00% 388 cSt 28.4 1.29Example 2 Total CAOS 0.00% 401 cSt 27.7 1.27 Comp Ex 3 Semi-batch 3.75%312 cSt 28.2 1.28

[0036] From above table, it is clear that the total CAOS process giveslow diol content, as compared to the semi-batch methodology. Since lowerdiol content corresponds to a lower dimethacrylate content, higherperformance in the Standard Slump Test is obtained with the macromonomerprepared by the total CAOS process, as compared with the resultsachieved using a macromonomer prepared by the non-CAOS process.

EXAMPLE 4 Preparation of Concrete Water Reducing Additive (WRA) fromMacromonomer B (A Total CAOS Product)

[0037] A 250 ml, 3 neck flask with a thermowell and side arm overflowtube was used. The working volume of the reactor was about 175 mL. Threedifferent feeds were co-fed to the reactor. The initiator, a 2.5%solution of ammonium persulfate in water, was fed from an ISCO pump at12.5 mL per hour. A mixture of 650 g Macromonomer B, 94.0 g acrylic acidand 456 g water was fed from a reservoir at 100 g/hour. The reactor wasinitially charged with 40 g distilled water and then the feeds werestarted and the reaction mixture was heated to 40° C. with continuousfeed for six hours. Reactor effluent collected during the first fivehours of operation was discarded. Product during the next two hours wascollected and evaluated in the slump test described below.

COMPARISON EXAMPLE 5 Preparation of Concrete WRA from Macromonomer C(Using a Semi-Batch Method).

[0038] A 250 mL, 3 neck flask with a thermowell and a side arm overflowtube was used. The working volume of the reactor was about 175 mL. Threedifferent feeds were co-fed to the reactor. The initiator, a 2.5%solution of ammonium persulfate in water, was fed from an ISCO pump at12.5 mL per hour. A 4.4% aqueous solution of mercaptoacetic acid was fedfrom a second ISCO pump at 12.5 mL per hour. A mixture of 650Macromonomer C, 94.0 g acrylic acid and 456 g water was fed from areservoir at 100 g/hour. The reactor was initially charged with 40 g ofdistilled water and then the feeds were started and the reaction mixturewas heated to 40° C. with continuous feed for six hours. Reactoreffluent collected during the first five hours of operation wasdiscarded. Product during the next two hours was collected and evaluatedin the slump test.

[0039] The Standard Slump Test:

[0040] The reaction products were tested in mortar mixes by using theslump test as described by ASTM method C-143. The method was modified inthis case by using mortar in place of concrete and the slump cone wasscaled by one-half in its dimension. In a typical test at a 25% watercut, 290 g water, 760 g cement and 1755 g dried mortar sand were mixedtogether with the admixture for 5 min and then the slump test wasperformed.

[0041] Comparison of the Slump Test Results for the WRA Made from thePolyether Methacrylates Prepared via Total CAOS and Semi-Batch ProcessesWater/ Wt % additive Additive Cement on dry cement Slump, mm Flow, mmNone 0.38 0    >20   NA Example 4 0.38 0.16 130 239 (total CAOSmacromonomer) Comparison 0.38 0.16 126 196 Example 5 (semi-batchmacromonomer)

[0042] Typically, higher slump and flow translate into higher waterreducing performance for the product. These results demonstrate that themacromonomer made through the total CAOS process, in accordance with thepresent invention, performs better as a WRA than the macromonomer madethrough the semi-batch process.

[0043] One or more embodiments of the present invention have beendescribed. Nevertheless, it will be understood that variousmodifications may be made without departing from the spirit and scope ofthe invention. Accordingly, other embodiments are within the scope ofthe following claims.

What is claimed is:
 1. An improved process for producing an alkoxylatedacrylate macromonomer or an alkoxylated methacrylate macromonomercomprising reacting, at a reaction temperature of between about 60° C.and about 130° C., a first component selected from the group consistingof hydroxyalkylacrylate, hydroxyalkylmethacrylate, and combinationsthereof, with a second component being an alkylene oxide compound, inthe presence of a double metal cyanide (DMC) catalyst, and optionally inthe presence of a solvent, wherein the first component is continuouslyadded to a reactor containing at least some amount of said secondcomponent, and wherein the first component and the second component areco-fed co-currently or counter-currently into the reactor.
 2. Theprocess of claim 1 wherein said alkylene oxide is selected from thegroup consisting of ethylene oxide, propylene oxide, butylene oxide, andcombinations thereof.
 3. The process of claim 1 wherein said catalyst isemployed in an amount of between 5 ppm and 500 ppm, based upon the totalamount of the reaction mixture.
 4. The process of claim 1 wherein saidcatalyst is employed in an amount of between 15 ppm and 150 ppm, basedupon the total amount of the reaction mixture.
 5. The process of claim 1wherein said reaction temperature is between about 60° C. and about 110°C.
 6. A process of producing a copolymer by reacting the macromonomer ofclaim 1 with a monomer selected from the group consisting of acrylicacid, methacrylic acid, fumaric acid, styrene, maleic acid, methylmethacrylate, and combinations thereof at a reaction temperature ofbetween about 0° C. and about 100° C.
 7. The process of claim 6 whereinsaid reaction temperature is between about 30° C. and about 60° C.
 8. Aprocess for making concrete using the copolymer of claim 6 as a waterreducing additive which comprises admixing cement, sand, water, and thecopolymer in order to form the concrete, said water being present in anamount less than the amount necessary to form concrete in the absence ofsaid copolymer.
 9. A process of producing water-dispersed polyurethaneusing the macromonomer of claim 1 comprising the steps of: (a)copolymerizing the macromonomer with an acid selected from the groupconsisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid,and combinations thereof, at a reaction temperature of between about 0°C. and about 100° C., to provide a copolymer containing hydroxylmoieties and acid moieties; and (b) reacting at least a portion of saidhydroxyl moieties on said copolymer with an isocyanate at an elevatedtemperature to produce a polyurethane containing at least a portion ofsaid acid moieties situate in a middle, hydrophobic polyether, portionof said polyurethane in order to impart a water-dispersiblecharacteristic to said polyurethane upon admixing said polyurethane withwater.